Dyestuffs of the anthraquinone series



Patented Apr. 7, 1942 1 OFFICE DYESTUFFS OF THE ANTHRAQUINONE SERIES William Dettwyler, Pitman, N. 3., assignor to E. I. du Pont de N emours 85 Company, Wilmington, DeL, a corporation of Delaware No Drawing. Application August 16, 1939, Serial No. 290,383

1 Claim.

This invention relates to the preparation of dyestuffs of the anthraquinone series, and more particularly to the preparation of new and valuable olive and gray to black dyestuffs of the benzanthronylanthraquinone-acridine series of the general formula:

mains intact and includes anthraquinone and its substitution derivatives except where a condensed ring is attached through the 9- or 10- position of the anthraquinone molecule.

The object of the invention is to prepare new gray dyestuffs which show increased fastness properties over the heretofore known benzanthronyl amino anthraquinone dyestuffs and which exhibit good tinctorial power dyeing cotton from the usual alkaline hydrosulfite vats in strong shades.

I have found that new olive and gray-to black dyestuffs may be prepared by condensing G-chloro-l-(Bz 1' benzanthronyl) aminoanthraquinone with aminoanthraquinones which may or may not contain simple monovalent or ring substituents, and then fusing the anthrimide compound thus formed with alkali to effect ring-closure of both imino groups to what are generally considered to be acridine .and carbazolerings. Y

The aminoanthraquinone compounds that may be condensed with the 6-ch1oro-1-(Bz-'1'-benzanthronyl)-aminoanthraquinone may carry such substituents as arylamino, alkyl or halogen radicals or additional rings such as illustrated by the aminoanthraquinone-benzacridone employed in the following examples. I

The following examples are given to illustrate the invention. The parts used are by weight.

Example 1 Thirty-one parts of Bz-l-bromobenzanthrone,

r 26 parts of 1-amino-6-chloroanthraquinone, 10 parts of soda ash and 1 part of cuprous chloride are refluxed in 400 parts nitrobenzene for 12 hours. 23 parts-bf l-aminoanthraquinone and 5 parts of soda ash are added and the heating (at reflux) continued for 16 hours. After cooling to room temperature, the product is filtered off, steam distilled to free it from nitrobenzene;v

25 filtered, washed with dilute hydrochloric acid, then with water and dried. It is a dark powder, soluble in concentrated sulfuric acid with. a

brown color. Twenty parts of this condensation product are introduced at 160 C. into a melt of parts caustic potash and 50 parts methanol. When the charge is completed, the temperature is raised to C. and held there for 1 hour.

The melt is then poured in 1000 parts of cold water, then boiled and the color isolated by fil- 3 tering, washing the cake alkali free and drying. The product is soluble in sulfuric acid with a green color. After pasting from sulfuric acid it dyes cotton in strong olive gray shades.

This product has, 40 the formula:

Example 2 Thirty-one parts of Bz-l-bromobenzanthrone, 26 parts of 1-amino-fi-chloroanthraquinone, 10

from an alkaline hydrosulfitevat I diamino-anthraquinone parts soda ash and 1 part of cuprous chloride are heated in 500 parts of nitrobenzene at reflux temperatures for 16 hours. 24 parts of 1:4-diaminoanthraquinone and parts of soda ash are then added and the mass is heated at reflux for 16 more hours. The condensation product which is isolated as in Example 1 is soluble in sulfuric acid with a green-black color.

Into a prepared melt of 100 parts of caustic potash and 50 parts of methanol, 25 parts of the above anthrimide are added at 160 C. and maintained at 175-180 C. for -1 hour. After dilution and boiling to precipitate the color it is filtered all and washed as in Example 1 and dried. It is a black powder soluble in sulfuric acid with a green color and dyes cotton'in greenblack shades. When the condensation is made with 1:5-diamino-anthraquinone instead of 1:4-

a somewhat shade is obtained. The products of this example have the general formula:

in which one X standsfor anamino group and the remaining X stands for hydrogen.

Example 3 Thirty-one parts of Bz-l-bromobenzanthrone are condensed in the usual manner in 400 parts one part of cuprousfchloride. amino 2:1(N) anthraquinone-benzacridone and 5 parts of soda ash are added and. the mass heated at reflux temperature for 16 hours. The

condensation product is isolated as in Example 1. It is a dark powder soluble in sulfuric acid redder with a brown color. When this product is fused amino 2:1 (N) -anthraquinone-benzacridone gives an olive dyestuff. The products of this example have the general formula: 7

in which one X and Y represent the benzecridone radical Y-HN and the remaining X and Y are hydrogen.

Example 4 6-chloro 1 (Bz-V-benzanthronyD-aminoanthraquinone prepared from 31 parts of Bz-lbromobenzanthrone and 26 parts of l-amin0-6- chloroanthaquinone without isolation are condensed with 31 parts of 1-amino-4-anilidoanthraquinone. After isolation as in Example 1, the anthrimide is a black powder soluble in sul-v furic acid with a blue color. Upon fusion in methanolic caustic potash a gray dyestufi is obtained which is soluble in concentrated sulfuric acid with a green color.

As illustrated in the above examples the ringclosure of the anthrimide compounds should be carried out in alcoholic caustic at temperatures of C. or higher. When lower temperatures are employed ring-closure of the alpha-betaanthrimide group may not take place, resulting in dyestuffs of different shades and dyeing properties.

I claim: The dyestuffs of the general formula in which one X and Y represent the benzacridone radical drosulfite vat in gray to olive shades. 

